Gluconic acid salts of certain aminemodified thermoplastic phenol-aldehyde resins, and method of making same



2,839,500 GLUCONIC ACID SALTS OF CERTAIN AMINE- MODIFIED THERMOPLASTIC PHENOL-ALDE- HYDE RESINS, AND METHOD OF MAKING SAME Melvin De Groote, St. Louis, Mo., assignor to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Original application January 26, 1953, Serial No. 333,386, now Patent No. 2,771,445, dated November 20, 1956. Divided and this application April 9, 1956, Serial No. 576,822

13 Claims. (Cl. 260-53) The present invention is a continuation-in-part of my five co-pending applications, Serial No. 288,742, filed May 19, 1952, now abandoned; Serial No. 296,083, filed June 27, 1952, now U. S. Patent 2,679,484; Serial filed July 30, 1952, Patent No. 2,743,251; Serial No.

Patent No. 2,771,440; and a division of my co-pending application Serial No. 333,386, 26, 1953, Patent No. 2,771,445.

My invention is concerned With new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the Water-in-oil type and particularly petroleum emulsions. My invention is also concerned with the application of such chemical products or compounds in various other arts and industries as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification. I

My aforementioned co-pending application, Serial No. 301,803, filed July 30, 1952, is concerned with the process of first condensing certain phenol-aldehyde resins, therein described in detail, with certain basic non-hydroxylated secondary mono-amines therein described in detail, and formaldehyde, which condensation is followed by oxyalkylation with certain monoepoxides, also therein described in detail.

The present invention is concerned with the aforementioned amino resin condensate in the form of a gluconic acid salt, i. e., a form in which all or part of the basic nitrogen atoms are neutralized With gluconic acid, i. e., converted into the salt of gluconic acid.

My aforementioned co-pending application, Serial No. 310,551, filed September 19, 1952, is concerned with a process for breaking petroleum emulsions of the waterin-oil type characterized by subjecting the emulsion to the action of a demulsifier including the amine resin condensates described in the aforementioned application Serial No. 301,803.

Needless to say, all that is required is to prepare the oxyalkylated amine resin condensates in the manner described in the two aforementioned co-pending applicand then neutralize with gluconic acid which, for practical purposes is as simple as analogous inorganic reactions.

dated March 7, Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

The present invention involves the surface-activity of the gluconic acid salts, i. e., either where only one basic acid salts may not necessarily be xylene-soluble. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable low molal alcohol, or amixture to dissolve the appropriate product being examined Weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest.

in the cmulsificationtest includes such obvious variant.

For convenience, what is vided into eight parts: i Part 1 is concerned with the general structure of the amine-modified resins which after oxyalkylation are converted to the gluconic acid salt;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin; a

Part 3 is concerned with appropriate basic secondary amines free from a hydroxyl radical which may be em ployed in the preparation modified resins;

Part 4 is concerned with reactions involving the resin,

of the herein described aminethe amine, and formaldehyde to produce specific products or compounds which are then subjected to cxyalkylation; Part 5 is concerned with the oxyalkylation of the -prod ucts described in Part 4 preceding;

Part 6 is concerned with the oxyalkylated derivatives describedin Part 5, preceding; in the corresponding salt of gluconic acid; t 1 Part 7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds orreaction products in the form of gluconic acid salts; and

Part 8 is concerned with uses for the products herein described, either assuch or after modification, including any applications-other than those involving resolution of petroleum emulsions of the water-in-oil type. This part is, limited also to the use of the gluconic acid salts. 1 For reasons which 'are obvious,'particularly for convenience and ease of comparison, the various parts are form as they appear in one or more of the aforementioned co-pending applications, to wit, Serial Nos. 288,742, 296,083, 301,803, 310,551, and 329,482. For example, Parts 1, 2, 3 and 4 are substantially as they appear in co-pending 329,482, filed January 2, 1953; Part 5 is substantially the same as it appears in aforementioned co-pending application, Serial No; 301,803, filed July 30, 1952, and Serial No. 310,551, filed September 19, 1952. Part 6 corresponds approximately to what appears in Serial No. 329,482, filed January 2, 1953.

and 296,083 to of the general structure of suchresins. These, resins ,may be exemplified by an idealized formula which may, in part, be an over-simplification in an effort to present certain resin structure. Such formulawould be the follow- Patented June 17, 1958 solvent, preferably a watersoluble solvent such as ethylene glycol diethylether or a and then mix with the equal It is understood the reference in thehereto appended claims as to the use of xylene said hereinafter will be gdi-- conversion of the basic application Serial No.

an aliphatic hydrocarbon substituent generally having four and not over 18 carbon atoms but most preferably not over 14 carbon atoms, and it generally is a small whole number varying from 1 to 4. In the resin structure it is shown as being derived from formaldehyde although obviously other aldehydes are equally satisfactory. The amine residue in the above structure is derived from a basic amine, and usually a strongly basic amine, and may be indicated thus:

/R HN in which R represents any appropriate hydrocarbon radical, such as an alkyl, alicyclic, arylalkyl radical, etc., free from hydroxyl radicals. The only limitation is that the radical should not be a negative radical, which considerably reduces the basicity of the amine, such as an aryl radical or an acyl radical. Needless to say, the two occurrences of R may jointly represent a single divalent radical instead of two monovalent radicals. This is illustrated by morpholine and piperidine. The introduction of two such amino radicals into a comparatively small resin molecule, for instance, one having 3 to 6 phenolic nuclei as specified, alters the resultant product in a number of ways. In the first place, a basic nitrogen atom, of course, adds a-hydrophile effect; in the second place, depending on the size of the radical R, there may be a counter-balancing hydrophobe effect or one in which the hydrophobe elfect more than counterbalances the hydrophileeffect of the nitrogen atom. Finally, in such cases where R contains one or more oxygen atoms, another effect is introduced, particularly another hydrophile elfect.

The resins employed as raw materials in the instant procedure are characterized by the presence of an aliphatic radical in the ortho or para position, i. e., the phenols themselves are difunctional phenols.

The resins herein employed contain only two terminal groups which are reactive to formaldehyde, i. e., they are difunctional from the standpoint of methylol-forming reactions. As is well known, although one may start with difunctional phenols, and depending on the procedure employed, one may obtain cross-linking which indicates that one or more of the phenolic nuclei have been converted from a difunctional radical to a trifunctional radical, or in terms of the resin, the molecule as a whole has a methylol-forming reactivity greater than 2. Such shift can take place after the resin has been formed or during resin formation. Briefly, an example is simply where an alkyl radical, such as methyl, ethyl, propyl, butyl, or the like, shifts from an ortho position to a meta position, or from a para position to a meta position. For instance, in the case of phenol-aldehyde varnish resins, one may prepare at least some in which the resins, instead of having only two points of reaction can have three, and possibly more points of reaction, with formaldehyde, or any other reactant which tends to form a methylol or substituted methylol group.

The resins herein employed are soluble in a nonoxygenated hydrocarbon solvent, such as benzene or xylene.

The resins herein employed as raw materials must be comparatively low molal products having on the average 3 to 6 nuclei per resin molecule.

The condensation products here obtained, whether in the form of the free base or the salt, do not go over to the insoluble stage on heating. The condensation product obtained according to the present invention is heat-stable and, in fact, one of its outstanding qualities is that it can be subjected to oxyalkylation, particularly oxyethylation or oxypropylation, under conventional conditions, i. e., presence of an alkaline catalyst, for example, but in any event at a temperature above 100 C. without becoming an insoluble mass.

in which R represents What has been previously said in regard to heat stability, particularly when employed as a reactant for preparation of derivatives, is still important from the standpoint of manufacture of the condensation products themselves insofar that in the condensation process employed in preparing the compounds described subsequently in detail, there is no objection to the employing of a temperature above the boiling point of water. As a matter of fact, all the examples included subsequently employ temperatures going up to C. to C.

What is said above deserves further amplification at this point for the reason that it may shorten what is said subsequently in regard to the production of the herein described condensation products.

Since formaldehyde generally is employed economically in an aqueous phase (30% to 40% solution, for example) it is necessary to have manufacturing procedure which will allow reactions to take place at the interface of the two immiscible liquids, to wit, the formaldehyde solution and the resin solution, on the assumption that generally the amine will dissolve in one phase or the other. Although reactions of the kind herein described will begin at least at comparatively low temperatures, for instance, 30 C., 40 C., or 50 (3., yet the reaction does not go to completion except by the use of the higher temperatures. The use of higher temperatures means, of course, that the condensation product obtained at the end of the reaction must not be heat-reactive. Of course, one can add an oxygenated solvent such as alcohol, dioxane, various ethers of glycols, or the like, and produce a homogeneous phase. If this latter procedure is employed in preparing the herein described condensations it is purely a matter of convenience, but whether it is or not, ultimately the temperature must still pass within the zone indicated elsewhere, i. e., somewhere above the boiling point of water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims, to the procedure employed in the process employed in the manufacture of the condensation product is not intended to limit the method or order in which the reactants are added, commingled or reacted. The procedure has been referred to as a condensation process for obvious reasons. As pointed out elsewhere it is my preference to dissolve the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However, all three reactants can he added in any order. I am inclined to believe that in the presence of a basic catalyst, such as the amine employed, that the formaldehyde produces methylol groups attached to the phenolic nuclei which, in turn, react with the amine, It would be immaterial, of course, if the formaldehyde reacted with the amine so as to introduce a methylol group attached to nitrogen which, in turn, would react with the resin molecule. Also, it would be immaterial if both types of compounds were formed which reacted with each other with the evolution of a mole of formaldehyde available for further reaction. Furthermore, a reaction could take place in which three different molecules are simultaneously involved although, for theoretical reasons, that is less likely. What is said herein in this respect is simply by way of explanation to avoid any limitation in regard to the appended claims.

PART 2 water-insoluble resin polymers of a composition approximated in an idealized form by the formula In'the above formula n represents a small whole number" varying from 1 to 6, 7 or 8, or more, up to probably or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated secondary amine as specified, following the same idealized lover-simplification previously referred to, the resultant product might be illustrated thus:

The basic nonhydroxylated amine may be designed thus:

In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine Without any amine in the reaction product, as indicated in the following formulas:

R1\ H 1 a-ss 1 R1 OH H OH R H H H sa as R R R As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde, or butyraldehyde. The resin unit may be exemplified thus:

OH I" OH 1 OH rr/ Rm...

in which R' is the divalent radical obtained from the particularaldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. .See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it 'is preferablethat the base be neutralized although I have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a, few lOths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have'the resin neutral. t

In preparing resins one does not =get1a singlepolymer,

i. e., one having just 3 units, or just 4 units,-or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentarner present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found no reason for using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized .in the following table: 7 i

TABLE I Mol. wt. Ex- Position R of resin ample R of R derived n molecule number om- (based on n+2) Phenyl Para... 3. 992.5

Tertiary bntyl do 3. 882. 5 Secondary butyl. Ortho. 3. 882. 5 Cyclohexyl Para 3. 1,025. 5 Tertiary amyl do"... 3. 959. 5 Mixed secondary Orth0. 3.

and tertiary amyl.

Tertiary amyl Nonyl Tertiary butyl Tertiary amyl 3. N onyl 3. Tertiary butyl 3.

23a Tertiary amyl 1, 24a Non 1, 25a Tertiary butyl. 1, 26a Tertiary amyl 1, 27a Nonyl l,

Tertiary amyL.

38a Amyl do 2. 39a Hexyl do 2. 40a OyclohexyL do-.- 2.

QQQ 90 OOQQrhQnbmd cn'orcu savior OIOIOI cncnmmcamm or EU'PART 3 As has. been pointed out previously, the amine herein employed as a reactant is a basic secondary monoamine, and preferably a strongly basic secondary monoarnine, free from hydroxyl groups whose composition is indicated thus:

in which R represents a monovalent alkyl, alicyclic, arylalkyl radical and may be heterocyclic in a few instances as inthe case of piperidine and a secondary amine derived from furfurylamine by methylation or ethylation, ora similar procedure.

Another example of a heterocyclic amine is, of course, morpholine.

The secondary amines most readily available are, of

course, amines such as dimethylamine, methylethylamine, diethylamine, dipropylamine, ethylpropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, and dinonylamine. Other amines include bis(1 ,3-dimethylbutyl)amine. There are, of course, a variety of primary amines which can be reacted with an alkylating agent such as dimethylsulfate, diethyl sulfate, an alkyl bromide, an ester of sulfonic acid, etc., to produce suitable amines within the herein specified limitations. For example, one can methylate alphaemethylbenzylamine, or benzylamine itself, to produce ,a suitable reactant. Needless to say, one can use secondary amines, such as dicyclohexylarnine, dibutylamine or amines containing one cyclohexyl group and one alkyl group, or one benzyl group and one alkyl group, such as ethylcyclohexyl amine, ethylbenzylamine, etc.

' Another class of amines which are particularly desirablefor the reason that they introduce a definite hydrophile effect by virtue of an ether linkage, or repetitious ether linkage, are certain basic polyether amines of the formula prior significance,particularly as a hydrocarbon radical.

The preparation of such amines has been described in the literature and particularly in two United States patents, to wit, U. S. Nos. 2,325,514 dated July 27, 1943, to

Hester, and 2,355,337 dated August 8, 1944, to Spence.

The latter patent describes typical haloalkyl ethers such I CHaOCaHiCl oHi-orn g, o n onioozrnootnrer 'Such hal oalkyl ethers can react with ammonia, or with a primary amine such as methylamine, ethylamine, cyclohexylamine, etc, to produce a secondary amine of the kind above described, in which one of the groups attached'to nitrogen is typified by R.

Such haloalkyl ethers also can be reacted with ammonia to give secondary amines as described in the firstof the two patents mentioned immediately preceding. Compounds so obtained are exemplified by Other somewhat similar secondary amines are those 0 p the composition as described in U. S. Patent No. 2,375,659 dated May 8, 1945, to Jones, et al. In the above formula R may be methyl, ethyl, propyl, 'amyl, octyl, etc.

Other amines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of 'cyclohexylmethylamine or the alkylation of similar primary amines, or for that matter, amines of the kind described in U. S. Patent No. 2,482,546 dated September 20, 1949, to Kaszuba, provided there is no negativc group or halogen attached to the phenolic nucleus. Examples include the following: beta-phenoxyethylaminc, garnma-phenoxypropylamine, beta-phenoxy-alpha-methylethylamine, and betaphenoxypropylamine.

Other suitable amines are the kind described in British Patent No. 456,5 l7 and may be illustrated by The products obtained by the herein described processes employed in the manufacture of the condensation product represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is diflicult to actually depict the final product of the cogeneric mixture except in terms of the process itself. The condensation of the resin, the amine and formaldehyde is described in detail in applications Serial Nos. 288,742 and 296,083, and reference is made to those applications for a discussion of the factors involved.

Little more need be said as to the actual procedure em ployed for the preparation of the herein described condensation products. The following example will serve by way of illustration:

Example 1b from a para-tertiary butylphenol and formaldehyde. The

resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes, the two external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the two external nuclei or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a, preceding, were powdered and mixed with an equal weight of xylene, i. e., 882 grams. The mixture was refluxed until solution was complete. It was then adjustedto approximately 30 C. to 35 C., and 146 grams of diethylamine added.

9 The mixture was stirred vigorously and formaldehyde added slowly. The formaldehyde was used as a 37% solution and 162 grams were employed, which were added in about 2 /2 hours. The mixture was stirred vig- PART 5 In preparing oxyalkylated derivatives of products of the kind which appear as examples in Part 3, I have oi'ously and kept within a temperature range of 30 to 5 found it particularly advantageous to use laboratory 45 C. for about hours. At the end of this period of equipment which permits continuous oxypropylation and time it was refluxed, using a phase-separating trap and oxyethylation. More specific reference will be made to a small amount of aqueous distillate withdrawn from treatment with glycide subsequently in the text. The time to time, and the presence of unreacted formaldehyde 1O oxyethylation step is, of course, the same as the oxynoted. .Any unreacted formaldehyde seemed to disappear propylation step insofar that two low boiling liquids are within 2 to 3 hours after refluxing was started. As soon handled in each instance. What immediately follows a the odor of formaldehyde was n longer detectible refers to oxyethylation and it is understood that oxythe phase-separating trap was set so as to eliminate all propylation can be handled convemently in exactly the water of solution and-reaction. After the water was 15 same manner. The oxyalkylation of the amine resin coneliminated part of the xylene was removed until the ns tes 18 carried out by procedures which are comtemperature reached approximately 145 C., or slightly mohly used the exyalkylatlon 0f oxyalkylahon S115- higher. The mass was kept at this higher temperature for eeptlble Ihflteflals- The feelers to e eohsldefed are about 4 hours and reaction stopped. During this time 2 discussed In some detall 1n pp Serial any additional water, which was probably water of mac 0 39 and 310,551 e reference 18 made f those l tion which had formed, was eliminated by means of the phcatlons for a descrlpllon of sultable eq p pr trap. The residual xylene was permitted to stay in the cautions to be taken and a general discussion of operating cogeneric mixture. A small amount of the sample was l qh The fehOWihg examples are glveh y y Of heated on a water bath to remove the excess xylene and lhush'ahoh- V the residual material was dark red in color and had the Example 16 consistency of a sticky fluid or tacky resin. The overall time for the reaction was about hours. In other ex- The oxyalkylatiomsusceptible compound employed is amples 1t Varied 24 hours to 36 Tlme h the one previously described and designated as Example he reduced by cumhg low temperature Penod to aPPT 30 lb. Condensate 1b was in turn obtained from diethylmately 3 t0 6 amine and the resin previously identified as Exam le 2a.

P Note that In Table II f01 1W1hg there are a large Reference to Table I shows that this particular resin is number of added P e llhlslfatlng the e P obtained from paratertiary butylphenol and formaldehyde. cedure. In each case the initial mixture was stirred and 05 pounds f hi resin condensate Wen dissolved in f at a y low temperature to for a 8.8 pounds of solvent (xylene) along with one pound of Perlod of Several, hours- Then refiuxlhg was p y finely powdered caustic soda as a catalyst. Adjustment 1111111 the Odor 0f fofmalfiehyde 'pp After f was made in the autoclave to operate at a temperature odor of formaldehyde disappeared the P P of approximately C. to C., and at a pressure trap was employed to separate out all the water, both the 40 f b t 15 t 20 pounds, solution and condensation. After all the water had been Thetime regulator was set so as to inject the ethylene Separated enough Xylene Was taken out to have the final oxide in approximately three hours and then continue product reflux for several hours somewhere in therange stirring for a half-hour or longer, The rea tion went; of 145 to 150 C., or thereabouts. Usually the mixture 45 readily and, as a matter of fact, the ethylene oxide could"v yielded a clear solution by the time the bulk of the water, have been injected in less than an hours time and probably' or all of the water, had been removed. the reaction could have been completed without allowing; Note that as pointed out previously, this procedure is for a subsequent stirring period. The speed of reaction,. illustrated by 24 examples in Table II. particularly at the low pressure, undoubtedly wasdue in a TABLE II Strength of Reac- Reac- Max. Ex. Resin Amt, Amine used and amount formalde- Solvent used tlon tion distill No. used grs. hyde $0111. and amt. temp, time, temp,

and amt. 0. hrs. O.

882 Dlethylamlne, 146 grams 37%, 162 g Xylene, 882 g. 3 150 480 Dlethylamlne, 73 grams 37%, 81 g.. Xylene, 480 g 24 152 633 do 30%,100g.. Xylene, 633 38 147 441 Dibutylamlne, 129 grams 81 g Xylene, 441 g 25-37 32 149 480 do do Xylene, 480 g 20-24 35 149 633 do o Xylene, 633 g. 18-23 24 150 882 Morpholine, 174 grams 37%, 162 g Xylene, 882 g 20-26 35 145 480 Morphollne, 87 grams 37%, 81 g.. Xylene, 480 g 19-27 24 156 9b 10a 633 .do d Xylene, 633 g 20-23 24 147 101) 13m... 473 Dioctylamine (dl2-ethylhexylamlne), 30%, 100 g... Xylene, 473 g. 2021 38 148 1lb.- 1411.--- 511 do .do Xylene, 511g- 1920 30 146 12b 1541.. 665 do 37%, 81 g Xylene, 685 g. 20-26 24 150 l3b. 2Cl 441 (OZH5002H4OC2H4)2NH,zmglams... 30%,100 g... Xylene, 441g. 20-22 31 147 1%.... 5a 480 (CZH6002H4OOZH4)2NH, 250 grams. d0 Xylene, 480 g 20-24 36 148 9a 595 (OZHBOOgHiOGiHiMNH, 250 grams 37%, 81 g Xylene, 595 g 23-28 25 145 441 (C4H90OH2OH(OH3)O(OH3)CHOH2)2NH, 361 grams --..do Xylene, 441 g 24 151 480 (O-lH9OOH2CH(CH3)O(O 3)CHCH2)2NH,361 grams 24 150 511 (O4H9OOH4CH(CH3)O(GH3)CHCH2)2NH,361grams 25 146 49s (01130011201120CH2CH2OCH2OH2)2NH,309 grams 37 24 542 (OHaOCHtCHzOCH2CH2OOH2OH2)2NH,3O9g1amS. 30 142 215-.-. 2511.--- 547 (CHaOCHZCHBOCH2CH2OOH OH2)fiNH, 309 grams- 26 14s 22b 2a..- 441 (CHaOCH2OH2OHzGH2CH2OH2hNH, 245 grams 28 143 235.... 26m... 595 (OHaOO 2OHIOH2OH2OH2OH2)2NH,245g18m8-.. 25 146 240---- 27a 891 (OHSOOHIOHgOHlOH2OH1OH2)2NH,98 grams 30%,50g 24 145 '11 large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 10.56 pounds. This represented a molal ratio of 24 moles of ethylene oxide per mole'of condensate.

The theoretical molecular weight at the end of the reaction period was 2112. A comparatively small example, less than 50 grams, was withdrawn easily for examination as far as solubility or emulsifying power was concerned and also for the purpose of making some tests on various oil-field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data, or subsequent data, or in the data presented in tabular form in subsequent Tables III and IV.

The size of the autoclave employed was 25 gallons. In innumerable comparable oxyalkylations I have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residue sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a different oxide.

Example 20 This example simply illustrates the further oxyalkylation of Example 10, preceding. As previously stated, the oxyalkylanon-susceptible compound, to wit, Example lb, present at the beginning of the stage was obviously the same as at the end of the prior stage (Example 1c), to wit, 10.56 pounds. The amount of oxide present in the initial step was 10.56 pounds, the amount of catalyst re mained the same, to wit, one pound, and the amount of solvent remained the same. The amount of oxide added was another 10.56 pounds, all addition of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 21.12 pounds and the molal ratio of ethylene oxide to resin condensate was 48 to 1. The theoretical molecular weight was 3163.

The maximum temperature during the operation was 125 C. to 130 C. The maximum pressure was in the range of 15 to 20 pounds. The time period was 3 /2 hours.

Example 3::

Example 40 The oxyethylation was continued and the amount of oxide added again was 10.56 pounds. There was no added catalyst and no added solvent. molecular weight at the end of the reaction period was 5280. The molal ratio of oxide to condensate was 96 to 1. Conditions as far as temperature and pressure were concerned were the same as in previous examples. The time period was slightly longer, to wit, 4 hours. The reaction unquestionably began to slow up somewhat.

Example 5 c The oxyethylation continued withthe introduction ofanother 10.56 pounds of' ethylene oxide. No added solvent was introduced and, likewise, no added catalyst The theoretical 12 was introduced. The theoretical molecular weight at the end of the agitation period was 6336, and the molal ratio of oxide to resin condensate was 124 to 1. The time period, however, had increased to 5 hours even though the operating temperature and pressure remained the same as in previous example.

Example 60 The same procedure was followed as in the previous examples except that an added pound of powdered caustic soda was introduced to speed up the reaction. The amount of oxide added was another 10.56 pounds, bringing the total oxide introduced to 63.36 pounds. The temperature and pressure during this period were the same as before.

Notwithstanding the addition of added caustic the time required for the oxyethylation was 5 hours. There was no added solvent.

Example 70 The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 72.93 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 84-48. The time required for the oxyethylation was a bit longer than in the previous step, to wit, 6 hours.

Example This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 85.48 pounds. The theoretical molecular weight was 9604. The molal ratio of oxide to resin condensate was 192. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was the same as in Example 70, preceding to wit, 6 hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series 'of four tables, Tables III and IV, V and VI.

In substantially every case a ZS-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a lS-gallon autoclave and then transferred to a 25-gallon autoclave. This is immaterial but happened to be a mater of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables III and IV, it will be noted that compounds 10 through 40c were obtained by use of ethylene oxide, whereas 416 through 800 were obtained by the use of propylene oxide alone.

Thus, in reference to Table III it is to be noted as follows The 6th column shows the amount of powdered caustic soda used as a camysasndihe 7th column shows the amount of solvent employed.

The 8th column can be ignored where a single oxide was employed.

The 9th column shows the theoretical molecular weight at the end of the oxyalkylation period.

The 10th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 10 coincides with the figure in column 3. 1

Column 11 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period.

Column 12 can be ignored insofar that no propylene oxide was employed.

Column 13 shows the catalyst at the end of the reaction period.

Column 14 shows the amount of solvent at the end of the reaction period.

Column 15 shows the molal ratio of ethylene oxide to condensate.

Column 16 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table VI. It is to be noted that the first column refers to Examples 10, 2c, 30, etc.

The second column gives the maximum temperature employed during the oxyalkyla-tion step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with several volumes of water, xylene and kerosene. "It sometimes happens that although xylene in comparatively small amounts will dissolve in the concentrated material, when the concentrated material in turn is diluted with xylene separation takes place.

Referring to Table IV, Examples 41c through 800 are the counterparts of Examples 10 through 400, except that the oxide employed is propylene oxide instead of ethylene oxide. Therefore, as explained previously, four columns are blank, to wit, columns 4, 8, l1 and 15.

Reference is now made to Table V. It is to be noted these compounds are designated by d numbers, 10!, 2d, 3d, ete., through and including 32d. They are derived, in turn, from compounds in the series, for example, 350, 39c, 53c and 620. These compounds involve the use or" both ethylene oxide and propylene oxide. Since compounds 11: through 400 were obtained by the use of ethylene oxide, it is obvious that those obtained from 350, through 390, involve the use of ethylene oxide first, and propylene oxide afterward. Inversely, those compounds obtained from 530 and 620 obviously came from a prior series in which propylene oxide was used first.

In the preparation of this series indicated by the small letter d, as 1d, 2d, 3d, etc, the initial 0 series such as 35c, 39c, 53c, and 620, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may have been the case in the original oxyalkylation step. Then oxyalkylation proceeded by using the sec-0nd oxide as indicated by the previous explanation, to wit, propylene oxide in 1d through 16d, and ethylene ox-ide in 17d through 32d, inclusive.

In examining the table beginning with 1d, it will be noted that the initial product, i. e., 350, consisted of the reaction product involving 10.5 pounds of the resin condensate, 15.84 pounds of ethylene oxide, 1.0 pound o caustic soda, and 8.8 pounds of the solvent.

It is to be noted that reference to the catalyst in Table V refers to the total amount of catalyst, i. e., the catalyst present from the first oxyalkylation step plus added catalyst, if any. The same is true in regard to the solvent. Reference to the solvent refers to the total solvent present, i. e., that from the first oxyalkylation step plus added solvent, if any.

In this series, it will be noted that the theoretical molecular weights are given prior to the oxyalkyl-ation step and after the oxyalkylation step, although the value at the end of one step is the value at the beginning of the next step, except obviously at the very start the value depends on the theoretical molecular weight at the end of the initial oxya-lkylation step; i. e., oxyethylation tor 1d through 16d, and oxypropylation for 17d through 32d.

It will be noted also that under the modal ratio the values of both oxides to the resin condensate are included.

The data given in regard to the operating conditions is substantially the same as before and appears in Table VI.

The products resulting from these procedures may contain modest amounts, or have small amounts, of the solvents indicated by the figures in the tables. If desired the solvent may be removed by distillation, and particularly vacuum distillation. Such distillation also may remove traces or small amounts of uncombined oxide, if present and Volatile under the conditions employed. I

Obviously, in the use of ethylene oxide and propylene oxide in combination one need not first use one oxide and then the other, 'but one can mix the two oxides and thus obtain what may be termed an indifferent oxyalkylation, i. e., no attempt to selectively add one and then the other, or any other variant.

Needless to say, one could start with ethylene oxide and then use propylene oxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, and then go back to propylene oxide; or, one could use a combination in which bu tylene oxide is used along with either one of the two oxides just mentioned, or a combination of both of them.

The colors of the products usually vary from a reddish amber tint to a definitely red, and amber. The reason .is primarily that no eifort is made to obtain colorless resins initially and the resins themselves may be yellow, amber, or even dark amber. Condensation of a nitrogenous product invariably yields a darker product than the original resin' and usually has a reddish color. The solvent employed, if xylene, adds nothing to the color but one may use a darker colored aromatic petroleum solvent. Oxyalkylation generally tends to yield lighter colored products and the more oxide employed the lighter the color of the product. Products can be prepared in which the final color is a lighter amber with a reddish tint. Such products can be decolorized by the use of clays, bleaching chars, etc. As far as use in demulsification is concerned,

p or some other industrial uses, there is no justification for the cost of bleaching the product.

Generally speaking, the amount of alkaline catalyst present is comparatively small and it need not be removed. Since the products per so are alkaline due to the presence of a basic nitrogen, the removal of the alkaline catalyst is somewhat more difficult than ordinarily is the case for the reason that if one adds hydrochloric acid, for example, to neutralize the alkalinity one may partially neutralize the basic nitrogen radical also. The preferred procedure is to ignore the presence of the alkali unless it is objectionable or else add a stoichiometric amount of concentrated hydrochloric acid equal to the caustic soda present.

TABLE VIContinued Max. Max. Solubility Ex. temp pres, Time, No. C p. s. 1. hrs.

Water Xylene Kerosene 10-15 1% Insoluble 10-15 13 .d 10-15 2 Emulsifiable. 10-15 3 .do 10-15 3 10-15 10-15 4% 10-15 10-15 21 Insoluble. 10-15 3 Dlsperslble. 10-15 3 Do. 10-15 3% Soluble. 10-15 4 Do. 10-15 4 Do. 10-15 4 Do. 10-15 Do.

5-10 1 Insoluble 5-10 1% D0. 5-10 1% Dispersible. 5-10 2 Soluble. 5-10 3 D0. 5-10 3 Do. 5-10 3% Do. 5-10 4 Do. 5-10 1 Insoluble. 5-10 1% o. 5-10 1% Dispersible. 5-10 1% Soluble. 5-10 2 D0. 5-10 3 D0. 5-10 4 D0. 5-10 5 DO. -15 1% Insoluble 10-15 2 D0. 10-15 2 Dlspersiblo. 10-15 3 D0. 10-15 5 Soluble. 10-15 3 Do. 10-15 3% Do. 10-15 4 Do. -20 1 Insoluble 1520 1% Do. 15-20 1% D0. 15-20 2% Dlsperslble 15-20 Do. 15-20 4 Soluble. 15-20 3V2 Do. 15-20 Do.

15-20 2 Insoluble. 15-20 2% Do. 15-20 Do. 15-20 4 Do. 15-20 2% D0. 15-20 2% Do. 15-20 D0. 15-20 3% Do. -25 D0. 20-25 1 D0. 20-25 1% Do. 20-25 2% 20-25 3 do Do. 20-25 4 Emulslfiable Do.

to insoluble. 20-25 4 .do Do. 20-25 5 Insoluble. Do. 20-25 .d0. Soluble. 20-25 do Do. 20-25 5 do Do. 20-25 Emulsiflablm. Do. 20-25 1% do Do. 20-25 2% do Do. 20-25 3% .do.. Do. 20-25 4 Soluble Do. 20-30 14 Insoluble. D0. 20-30 $6 do Do. 20-30 Emulsitlable-. Disperslble. 20-30 1% do Insoluble. 20-30 .d0 Do. 20-30 3 do D0. 20-30 4% Emulslfiable Do.

to soluble. 20-30 5 Soluble D0.

PART 6 Another factor which requires some consideration would The conversion of the oxyalkylated basic condensates of the kind previously described into the corresponding salt of gluconic acid is a simple operation since it is nothing more nor less than neutralization. The condensate invariably contains two basic nitrogen atoms. One can neutralize either one or both nitrogen atoms.

be the presence of basic catalysts which were used during the oxyalkylation process. Actual tests indicate that the basicity appears to be somewhat less than would be expected, particularly in examples in which oxyalkylation is comparatively high. The usual procedure has been to add enough gluconic acid to convert the product into the salt 21 as predetermined and then note whether or not the product showed any marked alkalinity. If so, slightly more gluconic acid was added until the product was either just barely acid or just very moderately alkaline. For sake of clarity this added amount of gluconic acid, if required, is ignored in the subsequent Table No. VIII.

Gluconic acid is available as a 50% solution. Dehydration causes decomposition. This is not true of the salts or, at least, the salts of the herein described oxyalkylated condensates. Such salts appear to be stable, or stable for all practical purposes, at least at a temperature slightly above the boiling point of water and perhaps at a temperature as high as 150 C. or thereabouts.

As has been pointed out previously the present application is a continuation-in-part of certain co-pending applications and reference is made to aforementioned copending application, Serial No. 329,482, filed January 2, 1953. The copending application, Serial No. 329,482, filed January 2, 1953, describes the neutralization of the nonoxyalkylated condensate. Reference now is made to Table VII which, in essence, is substantially the same as much of the data in Table II but includes additional calculations showing the amount of gluconic acid (50%) required to neutralize a certain amount of condensate for instance, compare Example 16 in Table VII with Example 112 in Table II. In any event since there were available various oxyalkylated derivatives of condensates 1b, 5b, 7b, and 11b these particular oxyalkylated derivatives were used for the purpose of illustrating a salt formation, all of which is illustrated in Table VIII.

Briefly stated, referring to Table VIII it is to be noted that l052grams of the nonoxyalkylated condensate required 780 grams of 50% gluconic acid for neutralization. Reference to Table VIII shows that 1052 grams of the condensate lb when converted into an oxyalkylated derivative as obtained from Example 3c were the equivalent of 5100 grams. Therefore, 5100 grams was ordinarily selected as the appropriate amount of oxyalkylated material for neutralization simply for the reason that calculation was eliminated.

The oxyalkylated condensate generally is a liquid and, as a rule, contains a comparatively small amount of solvent. Note the examples in Table VIII. The solvent happened to be xylene in this instance but could have been benzene, aromatic petroleum solvent, or the like. Needless to say, the solvent could have been removed from the oxyalkylated derivative by use of vacuum distillartion and this is particularly true if benzene happened to be the solvent. The product obtained from oxyalkylation is invariably lighter than the initial material for the reason that the condensate is dark colored and oxyalkylation simply dilutes the color. In other words, the product may be almost white, pale straw color or an amber shade with a reddish tint.

The product either before or after neutralization can be bleached with filtering clays, charcoals, etc. The procedure generally is, as a matter of convenience, to form the salt and then dilute with a solvent if desired, using such solvent as xylene or a mixture of two-thirds xylene and one-third ethyl alcohol or isopropyl alcohol, to give approximately a 50% solution. If there happened to be any precipitate the solution is filtered. If desired, the product prior to dilution could be rendered anhydrous simply by adding benzene and subjecting the mixture to reflux action under a condensate or a phase-separating trap. If there happened to be any tendency for the prodnot to separate then the solvents having hydrotropic properties, such as the diethylether of ethyleneglycol, or the like, are used.

The salt formation is merely a matter of agitation at room temperature, or at a somewhat higher temperature if desired, particularly in a reflux condenser. Usually agitation is continued for an hour but actually neutralization may be a matter of minutes. In some instances after salt formation is complete and the product is diluted to approximately 50%, I have permitted the solution to stand for about 6 to 72 hours. Sometimes, depending on composition, there is a separation of an aqueous phase or a small amount of salt-like material. On a laboratory scale the procedure is conducted in a separatory funnel. If there is separation of an aqueous phase, or any other undesirable material, at the bottom of the separatory funnel it is merely discarded. The salt form, of course, can be bleached in the same manner as previously described for the oxyalkylated derivative. Usually the color of the salt is practically the same as the oxyalkylated derivative. For various commercial purposes in which the product is used there is no justification for the added cost of decolorization. The salt form can be dehydrated or rendered solvent-free by the usual procedure, i. e., vacuum distillation, after the use of a phaseseparating trap.

The product as prepared, without attempting to de colorize, eliminate any residual catalyst in the form of a salt, and without any particular etfort to obtain absolute neutrality or the equivalent, is more than satisfactory for a number of purposes where the material is useful, such as application as a demulsifier for petroleum emulsions of the water-in-oil type, or oil-in-Water type; or in the prevention of corrosion of metallic surfaces, especially ferrous surfaces; or as an asphalt additive for anti-stripping purposes.

The condensates prior to oxyalkylation may be solids but are generally viscous liquids or liquids which are almost solid or tacky. Oxyalkylation reduces such materials to viscous liquids or thin liquids comparable to polygycols, of course depending primarily on the amount of alkylene oxide added. After neutralization the physical characteristics of the products are about the same and in the majority of cases are liquids. Needless to say, if a solvent were added, even if the material were solid initially, it would be converted into a liquid form.

In light of what has been said and the simplicity of salt formation it does not appear that any illustration is required. However, previous reference has been made i to Table VIII. The first example in Table VIII is Exto Example 1 Example 1 The salt was made from oxyalkylated derivative Example 3c. Oxyalkylated derivative 30, in turn was made from condensate Example lb. Condensate Example 1b, in turn, was made from resin Example 2a and diethylamine. 882 grams of the resin dissolved in an equal weight of xylene were reacted with 146 grams of diethylamine and 162 grams of 37% formaldehyde. All this has been described previously. The weight of the condensate on a solvent-free basis was 1052 grams. This represented approximately 27.8 grams of basic nitrogen. Referring to Table VIII it will be noted that 10.56 pounds of condensate lb were combined with 31.68 pounds of ethylene oxide in combination 8.8 pounds of solvent. In any event, 5100 grams of oxyalkylated derivative 30 were placed in a laboratory device which, although made of metal, was the equivalent of a separatory funnel. To this there was added 780 grams of gluconic acid and the mixture stirred vigorously for an hour and allowed to stand at room temperature, or slightly above, for approximately TABLE VII Salt formation calculated on Condensate in turn derived i'rombasis of non-oxyalkylated Salt condensate from Salt con- Ex. den- 37% Wt. 01 v N o. sate Amt. Amt. Amine formconden- Theo. 50% glu- No. Resin rcsin, Solvent sol- Amine used used, aldesate on basic conic N o. gins. vent, gms. hyde, solventnitrogen, acid, gms. gins. free basis, gins. gins.

gms.

882 Diothylamine 146 102 1, 052 27. 8 780 73 565 13. 9 390 73 1 100 718 13. 9 390 129 81 582 14. 390 129 81 621 14. 0 300 129 81 774 14. 0 390 174 162 1,080 28.0 780 87 81 579 14.0 300 87 81 732 14. 0 390 117 1 100 602 6. 8 190 117 1 100 640 6.8 190 117 81 794 6. 8 190 146 162 1, 052 27. 8 390 Dibutylamine. 129 81 582 14. 0 195 882 Morpholine 174 162 1,020 28.0 390 sol.

TABLE VIII Grams of oxyalkylated compound Obtained in turn from Percent which is equiv. percent Oxyalkylcondento grams of congluconic Ex. No. ated desate in densate acid to rivative, oxyalkylneutralex. No. ated deize, grams Conden- Amt. con- EtO PrO Solvent rivative Oxyelkyl- Condensate, densate, amt, amt., amt, ated cornsate ex. N0. lbs. lbs. lbs. lbs. pound 10. 56 8. 8 20. 6 5, 100 1, 052 780 10. 56 8. 8 l7. 3 6, 100 1, 052 780 10. 5o 8. 8 14. 6 7, 250 1, 052 7 12. 56 9.6 14. s 4, 200 e21 390 12. 5s 9. 6 12.8 4, 850 621 390 12. 56 9. 6 11.4 5, 425 621 390 10. 84 8. 8 12.7 8, 500 1, 080 780 10. 84 8. 8 99. 3 11, 600 1, 080 780 10. 84 8. 8 7. 8 13, 850 1, 080 780 12. 84 10. 2 17. 3 3, 700 640 190 12. 84 10. 2 14. 7 4, 350 640 100 12. 84 10.2 11.4 5, 600 640 190 10. 56 8. 8 18. 8 5, 600 1,052 780 10. 56 8. 8 17. 2 6, 125 1, 052 780 10. 56 8. 8 15.8 6, 675 1, 052 780 12 56 0. 6 8.9 7,000 6 390 12. 56 9. 6 8.2 7, 550 621 390 12. 56 9. 6 7. 5 8, 300 621 300 PART 7 Conventional demulsifying agents employed in the treatment of oil fieldemulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc, may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of my process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said materialor materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or .in a form exhibiting both oiland water-solubility. .Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or '1 to 20,000,01' l-to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to-the-material or materials of my invention when employed as demulsifying agents.

The materials of my invention, when employed as treating of demulsifying agents, are used in the conventional way, well known to the art, described, for example, in patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including hatch, continuous, and down-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mixing to stratify.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical dcinulsifier. A mixture which illustrates such combination is the following:

Glueonic acid salt, for example, the product of Example 13 20%;

A cyclohexylamine salt of a polypropylated napthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated napthalene monosulfonic acid, 24%;

. 25 A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%; Isopropyl alcohol, The above proportions are all weight percents.

PART 8 The gluconic acid salts herein described can be used as emulsifying agents for oils, fats and waxes; as ingredients in insecticide compositions; or as detergents and wetting agents in the laundering, scouring, dyeing, tanning and mordanting industries. They also can be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes. Also, the gluconic acid salts are useful in dry cleaners soaps.

Also, they may be used as additives in connection with other emulsifying agents; they may be employed to contribute hydrotropic effects; they may be used as antistrippers in connection with asphalts; they may be used to prevent corrosion particularly the corrosion of ferrous metals for various purposes and particularly in connection with the production of oil and gas, and also in refineries where crude oil is'converted into various commercial products. The products may be used industrially to inhibit or stop microorganic growth or other objectionable lower forms of life, such as the growth of algae, or the like; they maybe used to inhibit the growth of bacteria, molds, etc.; they are valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils, and also to hydraulic brake fluids of the aqueous or non-aqueous type; some have definite and anti-corrosive action. They may be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters.

After oxyalkylation a condensate of the kind previously described becomes a derivative which retains basic nitrogen radicals and also includes alkanol radicals, such as the hydroxyethyl or hydroxypropyl radical. Thus, in attempting to dehydrate the oxyalkylated salt derived from gluconic acid or merely by heating there may be a rearrangement wherein one forms the ester in the same manner that triethanolamine oleate can be converted into oleyl triethanolamine. Thus, the compounds described may serve as precursors for other derivatives obtained by esterification. In fact, any reference to decomposition on heating must of necessity include such possibility.

Having thus described my invention, what I claim as new and desire to obtain by Letters Patent, is:

1. A three-step manufacturing process including the method of first condensing (a) an oxyalkylation-susceptible, fusible, nonoxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substi- 26 tuted in the 2,4,6-positi0n; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehydederived methylene bridge connecting the amino nitrogen atom with a resin mole cute; and with the further proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

2. A three-step manufacturing process including the method of first condensing (a) an oxyalkylation-susceptible, fusible, nonoxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difun-ctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6-position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce 'a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the further proviso that the molar ratio of reactants be approximately 1, 2 and 2 respectively; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkyladon-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide,

glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

3. A three-step manufacturing process including the 7 method of first condensing (a) an oxyalkylation-susceptible, fusible, nonoxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substanc. i aaaaa tial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in that 2,4,6-position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate reactants have contributed part of the ultimate molecule 0 by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected fro-m the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide, and followed by the third step of neutralizing with gluconic acid.

4. A three step manufacturing process including the method of first condensing (a) an oxyethylation-susceptible, fusible, nonoxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forrning reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6-position; (b) a basic nonhydroxylated secondary monoarninc having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

5. A three-step manufacturing process including the method of first condensing (a) an oxyethylation-susceptible, fusible, nonoxygenated organic solvent-soluble, waterinsoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below C., with 'the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylanon-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methyl-glycide; and followed by the third step of neutralizing with glueonic acid.

6. A three-step manufacturing process including the method of first condensing (a) an oxyethylation-suscept'ible, fusible, nonoxygenated organic solvent-soluble, waterinsoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formal dehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a para-substituted aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms; (b) a basic nonhydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of Water and below 150 C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and 29 oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atom?v and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide; and followed by the third step of neutralizing with gluconic acid.

7. The manufacturing procedure of claim 1 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

8. The manufacturing procedure of claim 2 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

9. The manufacturing procedure of claim 3 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

10. The manufacturing procedure of claim 4 wherein 31) the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

11. The manufacturing procedure of claim 5 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

12. The manufacturing procedure of claim 6 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

13. The product resulting from the three-step manufacturing procedure defined in claim 1.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A THREE-STEP MANUFACTURING PROCESS INCLUDING THE METHOD OF FIRST CONDENSATING (A) AN OCYLALKYLATION-SUSCEPTIBLE, FUSIBLE, NONOXYGENERATED ORGANIC SOLVENT-SOLUBLE WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEINGG DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORM ING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 